CN101365538B - A bulk catalyst comprising nickel tungsten metal oxidic particles - Google Patents
A bulk catalyst comprising nickel tungsten metal oxidic particles Download PDFInfo
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- CN101365538B CN101365538B CN2006800398506A CN200680039850A CN101365538B CN 101365538 B CN101365538 B CN 101365538B CN 2006800398506 A CN2006800398506 A CN 2006800398506A CN 200680039850 A CN200680039850 A CN 200680039850A CN 101365538 B CN101365538 B CN 101365538B
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- catalyst
- metal
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- nickel
- mole
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- 239000003054 catalyst Substances 0.000 title claims abstract description 249
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 129
- 239000002184 metal Substances 0.000 title claims abstract description 129
- 239000002245 particle Substances 0.000 title claims abstract description 89
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 97
- 239000007787 solid Substances 0.000 claims abstract description 97
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 32
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 239000010937 tungsten Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000005323 carbonate salts Chemical group 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 46
- 230000008569 process Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 107
- 238000012360 testing method Methods 0.000 description 43
- 229910044991 metal oxide Inorganic materials 0.000 description 41
- 150000004706 metal oxides Chemical class 0.000 description 41
- 239000000725 suspension Substances 0.000 description 39
- 239000002253 acid Substances 0.000 description 37
- 238000010998 test method Methods 0.000 description 37
- 238000005987 sulfurization reaction Methods 0.000 description 36
- 239000000203 mixture Substances 0.000 description 33
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 32
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 31
- 229910000765 intermetallic Inorganic materials 0.000 description 31
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- 238000003756 stirring Methods 0.000 description 24
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- 238000010438 heat treatment Methods 0.000 description 23
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 22
- 238000005469 granulation Methods 0.000 description 21
- 230000003179 granulation Effects 0.000 description 21
- 229910052622 kaolinite Inorganic materials 0.000 description 21
- 238000007873 sieving Methods 0.000 description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 230000035484 reaction time Effects 0.000 description 17
- 239000010955 niobium Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 14
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
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- 150000001491 aromatic compounds Chemical class 0.000 description 9
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 238000013459 approach Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000018199 S phase Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 5
- -1 metals compound Chemical class 0.000 description 5
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000001694 spray drying Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 101000983970 Conus catus Alpha-conotoxin CIB Proteins 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
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- 239000003502 gasoline Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- USPVIMZDBBWXGM-UHFFFAOYSA-N nickel;oxotungsten Chemical compound [Ni].[W]=O USPVIMZDBBWXGM-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- 101000932768 Conus catus Alpha-conotoxin CIC Proteins 0.000 description 3
- 101000598987 Homo sapiens Medium-wave-sensitive opsin 1 Proteins 0.000 description 3
- 102100037812 Medium-wave-sensitive opsin 1 Human genes 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- 101001137074 Homo sapiens Long-wave-sensitive opsin 1 Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 150000001721 carbon Chemical class 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
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- 150000003658 tungsten compounds Chemical class 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- JVPGYYNQTPWXGE-UHFFFAOYSA-N 2-(4-methylphenyl)-1,3-benzothiazole Chemical compound C1=CC(C)=CC=C1C1=NC2=CC=CC=C2S1 JVPGYYNQTPWXGE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100255944 Arabidopsis thaliana RWA1 gene Proteins 0.000 description 1
- 101100255945 Arabidopsis thaliana RWA2 gene Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- DCGQUTJLMIWWSV-UHFFFAOYSA-N [W].[N+](=O)(O)[O-] Chemical compound [W].[N+](=O)(O)[O-] DCGQUTJLMIWWSV-UHFFFAOYSA-N 0.000 description 1
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B01J35/30—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention relates to a nickel tungsten bulk catalyst, to a process for the manufacture of the catalyst and to the use of the catalyst for the hydrotreatment, in particular the hydrodesulphurisation and hydrodenitrogenation of hydrocarbon feedstock. The catalyst comprises nickel tungsten metal oxidic particles obtainable by a process comprising forming a slurry of a first solid metal compound comprising Group VNI metal nickel and a second solid metal compound comprising Group VIB metal tungsten in a protic liquid, reacting the first and second solid metal compounds at elevated temperature whereby the first and second solid metal compounds remain at least partly in the solid state during the entire reaction to form the nickel tungsten oxidic bulk catalyst.
Description
The present invention relates to nickel tungsten body catalyst, be used for the hydrotreatment, particularly hydrodesulfurization of hydrocarbon raw material and the application of hydrodenitrogeneration for the manufacture of the method for described catalyst and described catalyst.
Body catalyst according to the present invention is generally the form of shaped particles, for example produces by the composition of extruding the additional materials, particularly adhesive material that contain metal oxide particle and 0～40wt% (with respect to the gross weight of body catalyst).Body catalyst is different from loaded catalyst, because it does not comprise preformed carrier material.Metal oxide is not to be deposited on the preformed carrier material, but exists as metal oxide particle.The further difference of body catalyst and loaded catalyst is, body catalyst contains at least metal oxide particle of 60wt% (based on the wt% of metal oxide with respect to the total weight of described body catalyst), and loaded catalyst has the metal oxide on the carrier material of being deposited on that significantly is lower than 60wt%.Described nickel tungsten body catalyst most preferably is bimetallic, and it in fact only contains tungsten as the group vib metal, also preferably only contains nickel as VIII family metal.The details of the composition of described body catalyst is described below.
Load type double-metal nickel tungsten catalyst and the application in the hydrotreatment of hydrocarbon raw material thereof are well known in the art already.GB 820536 has described a kind of method for the preparation of the high loaded catalyst particle of mechanical strength, described catalyst granules, contain the combination of cobalt, nickel, molybdenum, vanadium or tungsten, wherein, use the microsphere supported material of spray-dired hydrated alumina with the amount with respect to 60～90wt% of catalyst gross weight.For example, in embodiment 1, described a kind of nickel tungsten load type catalyst, it then obtains 566 ℃ of lower calcinings by extruding the wet cake that contains 83wt% carrier material and 17wt% metallic compound.
In the comparative example of the prior art that relates to trimetallic catalyst, also put down in writing bimetallic nickel tungsten body catalyst.They as one man are described to be inferior to three metal body catalysts that contain two kinds but not a kind of group vib metal is only arranged, and therefore are not applied in the hydroprocessing.
WO 00/41810 has described a kind of three metal body catalysts, particularly nickel/molybdenum that comprise the bulk catalyst particles that contains at least a VIII family's metal and at least two kinds of group vib metals/tungsten-based catalyst.Three metal body catalyst particles prepare in following methods, in the method, metallic compound is made up under the condition that has protic liquid, and during whole method, at least part of solid state that remains of one or more metallic compounds.Comparative examples A and B have described respectively nickel-molybdenum and nickel-tungsten body catalyst, and it is by making a kind of solid chemical compound that contains VIII family metal and a kind of dissolved compound that contains the group vib metal react to prepare.Compare with the bimetallic bulk catalyst described in the comparative example, described three metal body catalysts have significantly high catalytic activity.
WO 99/03578 has described the body catalyst that a kind of three metal hydrogenation are processed, and wherein, at least a portion but not every molybdenum in nickel molybdenum catalyst are replaced by tungsten.From molybdenum wolframic acid nickel (ammonium) precursor of solution, perhaps Direct precipitation prepares described catalyst from the insoluble slaine in the solution by decomposing (boiling is decomposed).With the bimetallic bulk catalyst (NH described in the comparative example
4NiMo-O and NH
4NiW-O) compare, resulting three metal body catalysts have significantly high catalytic activity, and this bimetallic bulk catalyst also is to decompose to prepare by the boiling of metal ammino-complex solution.
WO 2004/073859 has described a kind of bulk metal oxide catalyst, and it contains with one or more VIII family metals of oxide or sulphided form and one or more group vib metals, and the oxide of infusibility.This body catalyst is mainly nickel molybdenum bimetallic bulk catalyst, prepare by the following method: oxide material and the alkali compounds (compound that preferably contains ammonia) of control precipitation metallic compound, infusibility in protic liquid, form the ammino-complex of the oxide material of metal and infusibility, then heat this ammino-complex.Claim that the method causes obtaining to be essentially unbodied body catalyst, it is characterized in that: in x-ray diffraction pattern, do not have halfwidth less than or equal to 2.5 ° reflection peak (reflection).
WO 2005/005582 has described a kind of method for preparing lubricating base oil with the hydrotreatment body catalyst, and described body catalyst comprises the oxide with one or more VIII family metals of oxide or sulphided form and one or more group vib metals and infusibility.Described body catalyst is bimetal type in an embodiment, particularly nickel-molybdenum and nickel-tungsten, and by the following method preparation: after adding ammonium salt solution, a kind of solid chemical compound that contains VIII family metal and a kind of dissolved compound that contains the group vib metal are reacted.Described is that by XRD analysis, the structure of resulting oxide particle is unbodied.Remove sulphur from lubricating oil aspect, the nickel tungsten catalyst is better than nickel molybdenum catalyst.
EP 2005/004265 (undocumented) has described three metal body hydrogenation catalysts, and it contains VIII family metal (particularly molybdenum, tungsten or their mixture), group vib metal (particularly nickel, cobalt, iron or their mixture) and the V family metal (particularly niobium) of the metal molar ratio of regulation.The mol ratio of group vib metal and V family metal is preferably 0.3～3 in 0.1～1 scope.
WO 00/41811 has described a kind of three metal body hydrogenation catalysts and preparation method thereof, the method comprising the steps of: at least a VIII family metallic compound in the solution is mixed with two kinds of group vib metallic compounds in the solution at least and react, to obtain sediment.Compare with the bimetallic bulk catalyst (cobalt/molybdenum) described in comparative example 2, three metal body catalysts that obtain have significantly high catalytic activity, described bimetallic bulk catalyst prepares by the following method: the solution that will contain VIII family metallic cobalt joins in the solution that contains the vib metal molybdenum, forms the suspension of precipitated bulk catalyst particles.
The prior art list of references is as one man thought, compares with three metal body catalysts, and bimetallic bulk catalyst has low hydrodesulfurization activity.But trimetallic catalyst is compared from bimetallic catalyst has following shortcoming: owing to there being two kinds of different group vib metallic compounds, production process is more complicated.The in addition remarkable shortcoming of trimetallic catalyst is: be difficult to reclaim metal from the catalyst of lost efficacy (or using), because be difficult to separate with high yield two kinds of different group vib metals.Main purpose of the present invention provides a kind of have high hydrodesulfurization and the catalyst of hydrodenitrogenationactivity activity, and this catalyst can reach low-down residual sulfur in the raw material of processing, and can produce relatively simply and reclaim the composition metal.
According to the present invention, a kind of body catalyst that contains nickel tungsten metal oxidic particles is provided, this body catalyst can obtain by the method that may further comprise the steps:
(i) in protic liquid, formation contains the first solid metal compound of VIII family metallic nickel and contains the slurries of the second solid metal compound of group vib tungsten, and described slurries also contain less than the second group vib metal (with respect to the total amount of group vib metal) of 10 % by mole with less than 10 % by mole V family metal (with respect to the total amount of group vib metal);
(ii) described the first solid metal compound and described the second metallic compound are reacted, thus, at the first solid metal compound described in the whole course of reaction and at least part of solid state that remains of described the second solid metal compound, to form nickel tungsten oxide body catalyst.
Find unexpectedly, it is active that catalyst of the present invention has very high diesel hydrogenation for removal sulphur, and it is quite active with similar trimetallic catalyst, even better.In addition, the activity of hydrodenitrogeneration also is very high.
Nickel tungsten body catalyst is in fact bimetallic, and it in fact only contains tungsten as the group vib metal.Selectively, described body catalyst can contain the 2nd VIII family metal, cobalt for example, but most preferably, described body catalyst mainly only contain nickel as VIII family metal and tungsten as the group vib metal.Bimetallic bulk catalyst is different from three metal body catalysts, because it contains the second group vib metal (with respect to the total amount of group vib metal) less than 10 % by mole, and preferably in fact only contains a kind of group vib metal.Term " only has in fact a kind of group vib or VIII family metal " and refers to that catalyst does not most preferably contain other group vib or VIII family metal, but can contain a small amount of other group vib or VIII family metal, preferably less than 5 % by mole, be more preferably less than 3 % by mole, most preferably less than 1 % by mole (with respect to total amount of group vib or VIII family metal).Described catalyst can contain other metal.Selectively, described metal can also contain the V family metal (with respect to the total amount of group vib metal) that is lower than 10 % by mole.In concrete embodiment, body catalyst of the present invention contains V family metal, be preferably niobium, its amount is 0.1～10 % by mole (with respect to total amount of group vib metal), more preferably 0.1～9 % by mole, more preferably 0.1～8 % by mole, even more preferably 0.1～7 % by mole, most preferably be 0.1～5 % by mole.Find that V family metal has improved its activity, even when existing with relatively low amount.
In body catalyst of the present invention, the mol ratio of VIII family metal and group vib metal (below be called as the metal molar ratio), particularly the mol ratio of nickel and tungsten can change in wide scope in principle, and for example 0.1～5.Usually, than the catalyst that is 0.2～4, can obtain good result for metal molar.In this scope, two different subranges are distinguishing.It is 0.2～1 o'clock at the metal molar ratio, when under atmospheric pressure, making the reaction of the first and second metallic compounds, as if be difficult to obtain good catalyst, if not can not (in this article, good and refer to that better catalyst has hydrodesulfurization or the hydrodenitrogenationactivity activity high or higher than prior art).Under this metal molar ratio, XRD figure demonstrates a lot of peaks, may be because some raw materials still exist, but mainly be the crystal structure of undetermined non-active compound.
Find unexpectedly, it is 0.2～1 o'clock at the metal molar ratio, when the reaction that makes the first and second metallic compounds occurs under hydrothermal condition, can obtain good catalyst (in this article, good and refer to that better catalyst has than the high or higher hydrodesulfurization of prior art or hydrodenitrogenationactivity activity).Term " hydrothermal condition " refers to that reaction temperature is higher than the reaction condition of the boiling point of protic liquid.Refer under atmospheric pressure boiling temperature for boiling point.Find unexpectedly, with under the non-hydrothermal condition of atmospheric pressure with in addition compare than same catalyst prepared under the condition at lower metal molar, catalyst of the present invention has higher activity, particularly hydrodesulfurization activity.Usually, this condition has produced and has been higher than atmospheric pressure, and reaction is preferably carried out in autoclave, preferably carries out not needing to provide under the self-generated pressure of additonal pressure.Autoclave is the device that can bear pressure, and its design is used for heating liquid to the temperature that is higher than their boiling points.
Be in the preferred embodiment of water at protic liquid, hydrothermal condition refers to that pressure is higher than 1 Palestine and Israel and temperature is higher than 100 ℃.Because many reasons, water is the optimal selection of protic liquid.But, do not get rid of other protic liquid, therefore, " hydrothermal reaction condition " also comprises the reaction condition that uses the protic liquid outside dewatering in this article, and temperature is higher than the boiling point of described protic liquid, and pressure is higher than atmospheric pressure.Metal molar is than higher, and the result is better.Preferably, under these hydrothermal conditions, metal molar is preferably greater than 0.4 than greater than 0.3, more preferably greater than 0.5, and more preferably greater than 0.6, and most preferably greater than 0.7.
When metal molar than greater than 1 the time, use hydrothermal condition optional (but also being fine), therefore can Kaolinite Preparation of Catalyst under hydrothermal condition and atmospheric pressure, resulting catalyst is quite similar, although the inventor finds: when the reaction between the first and second metallic compounds is carried out under pressure is higher than the hydrothermal condition of 1 bar, the metal molar ratio is more than or equal to 1, and the activity of preferred 1～3 body catalyst is also slightly higher.Therefore, in an embodiment of the invention, body catalyst according to the present invention is produced in following methods: under hydrothermal condition, the reaction between the first and second metallic compounds is occured; Particularly produce in following methods: the protic liquid/solvent is water, is higher than under the hydrothermal condition that 100 ℃ and pressure is higher than 1 bar in reaction temperature described reaction is occured.Described reaction preferably in autoclave and spontaneous rising pressure and 110 ℃～170 ℃, more preferably 120 ℃～160 ℃, is more preferably carried out under 140～160 ℃ the temperature conditions.The applied metal mol ratio is 0.2～1.5, is preferably 0.2～1.3, more preferably 0.2～1.2, and the hydrothermal condition that most preferably is 0.2～1 metal molar ratio is favourable.
Consider from the angle of method economy, it is more attracting using the atmospheric pressure reaction condition.Therefore, preferred body catalyst according to the present invention has the metal molar ratio between 1～4, is preferably 1～2, most preferably is 1～1.5, and can obtains by the following method: wherein, substantially react under the atmospheric pressure.Usually, protic liquid is water, and the reaction temperature under atmospheric conditions is lower than 120 ℃, is usually less than 100 ℃.Carry out at elevated temperatures described reaction, preferably be higher than 50 ℃, more preferably be higher than 60 ℃, more preferably be higher than 70 ℃, most preferably be higher than 80 ℃.The inventor also finds: under the atmospheric reaction condition, by selecting metal molar than greater than 1, be preferably greater than 1.1, more preferably greater than 1.2, more preferably greater than 1.3, most preferably greater than 1.4, can obtain higher activity.But too high metal molar is not than being preferred, because this can cause the nickel compound reaction not exclusively.In order to prevent this problem, metal molar is lower than 2 than preferably, more preferably less than 1.5.
No matter be under hydrothermal reaction condition or under the atmospheric reaction condition, select the sufficiently long reaction time so that reaction is finished in fact.When the x-ray diffraction pattern of the metal oxide particle that separates did not demonstrate the reflection peak (reflection) of unreacted starting compound, reaction was carried out fully.In any case, select the reaction time, so that the final body catalyst after drying, shaping and calcining does not demonstrate the reflection peak of unreacted starting compound.Usually, this reaction was carried out 2 hours at least, and preferably at least 4 hours, more preferably at least 6 hours, most preferably at least 8 hours.Therefore the advantage of hydrothermal condition is that the reaction time is shorter, is lower than 8 hours or even to be lower than reaction time of 6 hours normally enough.
Can observe, body catalyst according to the present invention has metastable hexagonal structure, its x-ray diffraction pattern (angle of diffraction 2 θ) between 58 °～65 ° has single reflection peak, has the principal reflection peak between 32 °～36 ° and between 50 °～55 °.The X-ray powder diffraction pattern demonstrates close-packed hexagonal (cph) oxygen lattice, almost random distribution nickel and tungsten in the octahedral interstices of oxygen lattice, wherein a axle and b axle have with identical layer in close-packed hexagonal cph structure on two adjacent oxygen atoms between the length that conforms to of distance, the length of c-axis is the twice of the distance between two pantostrats in the close-packed hexagonal cph structure.The relevant lattice parameter of close-packed hexagonal cph or six side's nickel tungsten crystalline phases is: a=b=2.92 dust, c=4.64 dust (+/-0.02).
As if the existence of metastable hexagonal crystal phase represents the high catalytic activity of this oxide body catalyst, although do not find strict quantitative relationship.The physics reason of this correlation is not also fully understood or is known, and the inventor does not wish to be retrained and limit by theory yet.Therefore, the present invention for required protection body catalyst does not relate to about there being the described X-ray diffraction feature of metastable hexagonal crystal phase.Preferably, the reflection peak that in x-ray diffraction pattern, does not have in fact other crystalline compounds.It is generally acknowledged also and can have amorphous phase.
In body nickel tungsten catalyst, also do not determine metastable six side's phases.The x-ray diffraction pattern of the x-ray diffraction pattern of body catalyst of the present invention and the prior art three metal Ni/Mo/W body catalysts described in WO 00/41810 is similar, its difference is: the prior art diffraction pattern shows two peaks (bimodal Q) between 58 °～65 °, and demonstrates single reflection peak between approximately 63 °～65 ° according to metastable state six side's phase structures of nickel tungsten catalyst of the present invention.Opposite with prior art WO 2004/073859, the prior art has been described unbodied in fact NiMo bimetallic catalyst, observablely be, in catalyst of the present invention, high activity with exist metastable six sides mutually relevant; And opposite with the prior art, find good activity in following body catalyst: this body catalyst has such x-ray diffraction pattern, and the halfwidth [FWHM] that namely has a principal reflection peak is less than 2.5 ° well-developed principal reflection peak.This means that metastable six side's phase 3-D cph lattices are limited well.As if although metastable six sides also are crystal habits mutually, it also contains in the octahedral interstices of oxygen lattice the almost disordered state of the nickel of random distribution and tungsten.When in this article expression " transformed to crystal structure ", the meaning referred to the crystal structure except metastable six sides phase.
The metal oxide particle of discovery in body catalyst of the present invention is responsive especially for heat treatment.Importantly, make body catalyst carry out heat treated being lower than under the temperature that the temperature that transforms to crystal structure occurs.Under high-temperature T, six side's phases and/or amorphous phase are converted into " rule " rhombic system nickel tungsten oxide NiWO
4, it can by with the standard powder diffraction data: JCPDS-ICDD PDF card15-0755 or 72-1189 or 72-0480 compare to determine.This is applicable to any and all heat treatment step in the preparation method of body catalyst.This also is specially adapted to the heat treated of the body catalyst of the shaping after compound and shaping.Preferably, body catalyst carries out heat treated being lower than under 450 ℃ the temperature, more preferably less than 400 ℃, more preferably less than 375 ℃, most preferably is lower than 350 ℃.
Being considered to necessary for body catalyst of the present invention is, makes all at least part of solid states that remains of the first and second solid metal compound in whole course of reaction, to form nickel tungsten oxide body catalyst.Term " at least part of solid state that remains " refers to that at least part of metallic compound exists as solid metal compound, and selectively, the part metals compound exists as the solution of this metallic compound in protic liquid in addition.Solid this technique is called as solid-technique, and as preparing three metal body catalysts several a kind of being recorded among the WO 00/41810 in may the preparation approach.The bimetallic catalyst that is recorded among the Comparative Examples B of WO 00/41810 prepares in following methods, wherein only makes at least part of solid state that remains of nickel compound in whole course of reaction.Find: as confirming among the embodiment, the solid of the prior art-dissolved matter approach causes quite low activity.
After reactions steps, metal oxide particle preferably has the median particle diameter at least 0.5 μ m scope, more preferably at least 1 μ m, most preferably at least 2 μ m still preferably are no more than 5000 μ m, more preferably no more than 1000 μ m, even more preferably no more than 500 μ m, be most preferably not exceeding 150 μ m.Even more preferably, median particle diameter is in the scope of 1-150 μ m, most preferably in the scope of 2-150 μ m.Preferably, compound and be shaped after, the average grain diameter of metal oxide particle remain unchanged in fact (by measuring size distribution near light forescatering method).
This body catalyst contains at least metal oxide particle of 60wt% (based on the wt% of metal oxide with respect to the total weight of described body catalyst), these are different from loaded catalyst, and wherein said loaded catalyst has deposited the metal oxide that significantly is lower than 60wt% at its carrier material.In order to obtain high catalytic activity, preferably, body catalyst of the present invention contains at least metal oxide particle of 70wt%, and more preferably 75wt% at least is more preferably at least 80wt%, most preferably 85wt% at least.Its surplus 0～40wt% can be that one or more are selected from following group material: adhesive material, conventional hydrotreating catalyst, acid accelerator and cracking solution compound.Usually, make described metal oxide particle and adhesive material compound after, described composition is shaped, preferably be extruded, with the bulk catalyst particles of forming shaped.In the body catalyst that is shaped, preferably metal oxide particle and adhesive material are made up, to improve the side crushing strength of the particle that is shaped.The invention still further relates to the bulk catalyst particles of the shaping that contains metal oxide particle.Selectively, this metal oxidic bulk catalyst particles can be directly used in hydroprocessing technique, does not namely need substantial combination and shaping.For this purposes, preference as by the sieve or the cohesion process as described in particle, to obtain narrower size distribution.The invention still further relates to the application of metallic catalyst of the present invention in the slurry hydroprocessing technique, the metal oxidic bulk catalyst particles that substantial combination and shaping are not carried out in preferred use.
Preferably, preferably after combination and being shaped, when measuring by the BET method, body catalyst of the present invention has at least 10m
2The BET surface area of/g, more preferably 50m at least
2/ g, most preferably 80m at least
2/ g.The mean pore sizes of metal oxide particle (50% pore volume is lower than described diameter, other 50% greater than described diameter) is preferably 3～25nm, and more preferably 5～15nm (passes through N
2Desorption method is measured).When passing through N
2During determination of adsorption method, the total pore volume of described metal oxide particle is preferably at least 0.05ml/g, more preferably 0.1ml/g at least.
Desirable is that after compound and shaping, the pore-size distribution of body catalyst of the present invention is preferably approximately identical with conventional hydrotreating catalyst.More specifically, when passing through N
2When desorption method was measured, metal oxide particle preferably had the mean pore sizes of 3～25nm; When passing through N
2During determination of adsorption method, pore volume is 0.05-5ml/g, is preferably 0.1-4ml/g, and more preferably 0.1-3ml/g most preferably is 0.1-2ml/g.
Usually, compound and be shaped after, body catalyst of the present invention has the mechanical strength (with side crushing strength (SCS) expression) that is at least 1lbs/mm, is preferably 3lbs/mm at least (be that the extrudate of 1～2mm measure with diameter).Undertaken compoundly by the adhesive material with metal oxide particle and q.s, can suitably improve the SCS of described body catalyst.
In order to obtain having the carbon monoxide-olefin polymeric of high mechanical properties, for carbon monoxide-olefin polymeric of the present invention, it is desirable having low macroporosity.Preferably, the pore volume of the carbon monoxide-olefin polymeric less than 30% is diameter greater than the hole of 100nm (measuring contact angle: 140 ° by mercury injection method), is more preferably less than 20%.
The invention still further relates to the body catalyst of sulfuration, it comprises sulfureted body catalyst of the present invention.The invention still further relates to above-mentioned bulk catalyst composition or sulfuration body catalyst comprise the hydrocarbon raw material of sulfur-bearing and nitrogen organic compound for hydrotreatment application, and the method that is used for the hydrocarbon raw material of ultra-deep hydrodesulfuration sulfur-bearing and nitrogen, the method comprises: raw material is contacted with the body catalyst of (not) of the present invention sulfuration.
The nickel tungsten catalyst of considering the Comparative Examples B among the WO 00/41810 has quite low activity (by the DBT measuring), find surprisingly: nickel tungsten body catalyst of the present invention has very high activity, and allows to reach low-down sulfur-bearing level in the raw material of the nitrogenous and sulphur of hydrotreatment reality.Seem, for the hydrocarbon raw material that also contains nitrogen except sulphur compound of reality, it is best that the DBT method of testing must not demonstrate this catalyst.Do not wish to be bound by theory, it is generally acknowledged: catalyst of the present invention not only is good at removing sulphur, and more is good at removing nitrogen.Remove nitrogen and can prevent that catalyst from being adsorbed by force nitrogen compound and poisoning, and prevent that the removal S activity that causes obtaining low-residual sulphur level is lowered.
Term " hydrotreatment " is included in all techniques that make hydrocarbon raw material and H-H reaction under the pressure of the temperature of rising and rising in this article, comprises hydrogenation, hydrodesulfurization, hydrodenitrogeneration, HDM, hydrogenation aromatics-removing, hydroisomerization, Hydrodewaxing, hydrocracking and in the hydrocracking (it is commonly called the mild hydrogenation cracking) that relaxes under the press strip spare.Carbon monoxide-olefin polymeric of the present invention is particularly suitable for the hydrotreatment hydrocarbon raw material.This hydroprocessing technique comprises: for example, and the hydrodesulfurization of hydrocarbon raw material, hydrodenitrogeneration and hydrogenation aromatics-removing.Suitable raw material is: for example, and intermediate oil, kerosene, naphtha, decompression diesel oil and heavy diesel fuel.Can adopt conventional process conditions, for example temperature is between 250 ℃～450 ℃, and pressure is between the 5-250 bar, and air speed is at 0.1-10h
-1Between, H
2/ oil ratio example is between 50-2000Nl/l.
Body catalyst of the present invention can be used for nearly all hydroprocessing technique and process plurality of raw materials under the reaction condition of wide region, for example temperature is between 200 ℃～450 ℃, Hydrogen Vapor Pressure between 5～300 bar, fluid per hour air speed (LHSV) at 0.05～10h
-1Between.
Nickel tungsten body catalyst of the present invention is particularly suitable for the ultra-deep hydrodesulfuration of diesel raw material.The activity of finding nickel tungsten body catalyst of the present invention is directly proportional with hydrogenation technique pressure.Because this point, under high pressure, the advantage of high catalytic activity and low-down sulphur residual level even more important.Being higher than 20 bar, more preferably be higher than 30 bar, be more preferably and be higher than 40 bar, most preferably be higher than under the pressure of 50 bar, obtain excellent especially result.Therefore, catalyst of the present invention most preferably is used for hydrodesulfurization and the pretreated technique of hydrodenitrogeneration to the feed stream of hydrocracking, perhaps for the preparation of the technique of lubricant (=lubricating oil).
After processing with catalyst hydrogenation desulfurization of the present invention, the sulphur residual level is usually less than 30ppmwt, preferably is lower than 20ppmwt, more preferably less than 10ppmwt, most preferably is lower than 5ppmwt.Nitrogen residual level even lower preferably is lower than 15ppmwt, more preferably less than 10ppmwt, more preferably less than 5ppmwt, most preferably is lower than 3ppmwt.In order to realize that the sulphur residual level is lower than 10ppmwt and the nitrogen residual level is lower than 3ppmwt, the higher hydrotreatment pressure of preferred use preferably is higher than 20 bar, more preferably is higher than 30 bar, most preferably is higher than 40 bar.
The invention still further relates to the method for the preparation of body catalyst of the present invention, it comprises:
(i) in protic liquid, formation contains the first solid metal compound of VIII family metallic nickel and contains the slurries of the second solid metal compound of vib metal tungsten, and described slurries also contain less than the second group vib metal (with respect to the total amount of group vib metal) of 10 % by mole with less than 10 % by mole V family metal (with respect to the total amount of group vib metal);
(ii) at elevated temperatures, described the first solid metal compound and described the second solid metal compound are reacted, thus at the first solid metal compound described in the whole course of reaction and at least part of solid state that remains of described the second solid metal compound, to form nickel tungsten oxide body catalyst;
Selectively, described method also comprises one or more following steps:
(iii) metal oxide particle is separated from described slurries;
(iv) before making metallic compound combination and/or reaction, during or afterwards, making itself and gross weight with respect to described body catalyst is one or more combinations of materials of following group of being selected from of 0～40wt%: adhesive material, conventional hydrotreating catalyst and cracking compound;
(v) spray-drying, (fast) drying, grinding, kneading, slurry mixing, dry type mixing or wet mixed or their combination;
(vi) be shaped; And
(vii) being lower than the temperature that occurs to the crystal structure conversion, preferably be lower than under 350 ℃ drying and/or heat treatment.
A kind of as among the preparation method of various body catalyst, Gu of the present invention solid-technique is recorded in detail among the WO 00/41810, is introduced in this mode by reference.
Step (i)
The protic liquid that is applied in the inventive method can be any protic liquid.The example has water, carboxylic acid and alcohol, for example methyl alcohol, ethanol or their mixture.As the protic liquid of the inventive method, the preferred liquid that contains water, for example mixture of alcohol and water, the more preferably water of using.Different protic liquid also can be applied in the method for the present invention simultaneously.For example, the suspension of metallic compound in ethanol can be joined in the water slurry of another metallic compound.Usually, select not can disturbance reponse protic liquid.If described protic liquid is water, at least part of solubility for the VIII family non-precious metal compound of solid state and group vib metallic compound generally is less than 0.05mol/ (in 18 ℃ of lower 100ml water) in the method for the invention.
If described protic liquid is water, at least part of for the suitable nickel compound of solid state comprises in course of reaction, and more preferably basically formed by following: oxalates, nitrate, carbonate, subcarbonate, hydroxide, molybdate, phosphate, tungstates, oxide or their mixture; Basic nickel carbonate, nickel hydroxide, nickelous carbonate or their mixture are most preferred.Usually, the mol ratio of hydroxyl group and carbonate is preferably 0～2 in the basic nickel carbonate in 0～4 scope, and more preferably 0～1, most preferably be 0.1～0.8.
At least part of for the suitable tungsten compound of solid state comprises water-fast tungsten compound during method of the present invention, for example tungsten dioxide and tungstic acid, tungsten sulfide (WS
2And WS
3), tungsten carbide, positive wolframic acid (H
2WO
4H
2O), nitric acid tungsten, aluminum tungstate (also having metatungstic acid aluminium or many aluminum tungstates), ammonium phosphotungstate or their mixture; Positive wolframic acid and tungsten dioxide and tungstic acid are preferred.
Preferably, the reaction between the first metallic compound and the second metallic compound is acid/alkali reaction, and described the first metallic compound or described the second metallic compound are alkali solids, and another metallic compound is acid solid chemical compound.
In the most preferred embodiment of the inventive method, the first solid metal compound and the second solid metal compound do not contain nitrogen-atoms, and at step I ii) at least part of the re-using of protic liquid of separating with reacted metal oxide particle, with in step I) in form slurries.Most preferably, in the method, the first metallic compound is (alkali formula) nickelous carbonate, and the second metallic compound is tungsten oxide or wolframic acid.
Owing to several reasons, the method satisfies the highest standard of the Catalyst Production of environmental friendliness and economic optimization.Except metallic compound does not contain the nitrogen-atoms, as for example described in the WO 2004/073859, this reaction does not need to add ammoniacal liquor in reactant mixture yet, so the method does not have nitrogen-atoms fully.When repetitive cycling, in described protic liquid, there is not the accumulation of foreign ion such as ammonium ion and/or nitrate ion, needn't be strict with the oxide particle of the resulting separation of washing; Owing to having reduced the loss of heavy transition metal, therefore having had low environmental hazard; There is not the explosion danger that causes owing to forming ammonium salt yet.In addition, because described catalyst is bimetallic, the chemical property in the reactions steps is simpler, and because only have a kind of group vib metal, when reclaiming the liquid that separates after reaction, can not have departing from of group vib metal composition.Because at least part of solid state that remains of compound in whole course of reaction, the amount of metal that is dissolved in the described protic liquid is less, and therefore loss is lower.And because do not need to separate two kinds of group vib metals, the bimetallic catalyst of inefficacy is easier to reclaim it than trimetallic catalyst and forms metal, and the recovery of trimetallic catalyst is very difficult.Can use the conventional method of separating nickel and tungsten.This is being favourable aspect complexity that reduces recovery technique, cost and the raising metal recovery rate.
In order to obtain having the final carbon monoxide-olefin polymeric of high catalytic activity, preferably, the first and second solid metal compound are porous metals compounds.For the first metallic compound, be preferably basic nickel carbonate, its surface area (SA): SA＞220m
2/ g, pore volume pV＞0.29cm
3/ g (measuring by the nitrogen adsorption method), mean pore sizes MPD＞3.8nm (measuring by the nitrogen desorption method); For the second metallic compound, be preferably wolframic acid, SA＞19m
2/ g, pV＞0.04cm
3/ g, MPD＞6.1nm.Desirablely be the total pore volume of these metallic compounds and pore-size distribution and conventional hydrotreating catalyst similar.Preferably, when measuring by mercury or water voids rate determination method, pore volume is 0.05-5ml/g, is preferably 0.05-4ml/g, and more preferably 0.05-3ml/g most preferably is 0.05-2ml/g.In addition, when measuring by the BET method, surface area is preferably at least 10m
2/ g, more preferably 20m at least
2/ g, and most preferably be at least 30m
2/ g.
Preferably in the scope of at least 0.5 μ m, more preferably at least 1 μ m most preferably is at least 2 μ m to the median particle diameter of the first and second solid metal compound, but preferably be no more than 5000 μ m, more preferably no more than 1000 μ m, even more preferably no more than 500 μ m, be most preferably not exceeding 150 μ m.Even more preferably, average grain diameter is in 1-150 μ m scope, most preferably in 2-150 μ m scope.Usually, the granularity of metallic compound is less, and their reactivity is higher.Therefore, the metallic compound that has a particle diameter that is lower than the preferred lower limit value is preferred embodiment of the present invention in principle.But because health, safety and environment reason, processing so little particle needs special precautionary measures (by measuring size distribution near light forescatering method).
Step (ii)
In their adition process and/or afterwards, make slurries under reaction temperature, keep a period of time, occur to allow reaction.Usually, during reactions steps, make slurries remain its natural pH value.Especially, opposite with WO 2004/073859, preferably do not add ammonium salt.The pH value is preferred in the scope of 0-12, more preferably in the scope of 3-9, most preferably in the scope of 5-8.As mentioned above, must be noted that and select by this way pH value and temperature: namely metal not exclusively dissolves during reactions steps.Gu in solid-technique, the amount of protic liquid is not crucial, can select easily enough low amount can produce necessarily waste liquid, condition is to exist the solvent of q.s can stir well to guarantee slurries.In addition, be under the very active and/or partly soluble situation at raw material, should prevent raw material already tempestuously reaction during adding.This can realize by the amount that for example improves solvent or the temperature that reduces mixed material again.
For the performance of body catalyst of the present invention very important parameter, particularly reaction temperature and pressure, metal molar ratio, hydrothermal reaction condition and reaction time, all at length be recorded in the specification of described body catalyst.As mentioned above, necessaryly in the method for the invention be, when metal molar than between 0.2～1 the time, this reaction preferably surpasses under 100 ℃ of hydrothermal conditions with high 1 bar of pressure in reaction temperature to be carried out.When metal molar than greater than 1 the time, in order can to obtain a little more high activity or to use lower nickel mol ratio or make reaction quicker, the catalyst of gained is also preferably produced under hydrothermal condition.But, consider simplicity and the economy of technique self, described body catalyst can (and preferred) be prepared in following technique: wherein, make and react substantially atmospheric pressure and be lower than 120 ℃, preferably be lower than under 110 or 100 ℃ the temperature and carry out.
Step (iii)
After reactions steps, if necessary, can be with resulting metal oxide particle and fluid separation applications, for example by filtering or spray-drying.In another embodiment, use quite a small amount of protic liquid, to such an extent as to there is not liquid from solid reaction product, to separate.As described below randomly make up with additional materials after, wet product is formed, then dry.For the separating metal oxide particle, any solid-liquid isolation technics can be used in principle.Can with additional materials combination before or after carry out described the separation.At the solid-liquid after separating, selectively, can comprise washing step.In addition, after optional solid-liquid separation and drying steps, and before making up with additional materials, can the described body catalyst of heat treatment.
Step (iv)
If necessary, can in the process of above-mentioned preparation metal oxide particle, add additional materials, perhaps after preparation, additional materials is joined in the metal oxide particle, described additional materials is selected from adhesive material, conventional hydrotreating catalyst, cracking compound, acidic promotor, for example fluoridizes the group of phosphorus (phosphorusof fluorine) or its compositions of mixtures.Preferably, after the preparation metal oxide particle and before separating step, still in any case before forming step, this additional materials is joined in the slurries.At after separating from the liquid of mixing/kneading step, mostly this additional materials is added.Can be recorded among the WO 00/41810 with the example of other additional materials of metal oxide particle of the present invention combination.
In all above-mentioned technique alternatives, term " makes body catalyst and combination of materials " and refers to described material is joined in the described body catalyst, otherwise perhaps; Then resulting composition is mixed.Preferably mix (" wet mixing is closed ") existing under the condition of liquid.This has improved the mechanical strength of final carbon monoxide-olefin polymeric.Make the combination of described metal oxide particle and described additional materials, and/or the described material of adding causes body catalyst to have extra high mechanical strength in the process of preparation metal oxide particle, if particularly the median particle diameter of metal oxide particle (by measuring size distribution near light forescatering method) is in the scope of at least 0.5 μ m, more preferably at least 1 μ m, at least 2 μ m most preferably, but preferably be no more than 5000 μ m, more preferably no more than 1000 μ m, more preferably no more than 500 μ m, be most preferably not exceeding 150 μ m.Even more preferably, median particle diameter is in the scope of 1-150 μ m, most preferably in the scope of 2-150 μ m.Make the combination of described metal oxide particle and described additional materials cause making described metal oxide particle to be embedded in this material, perhaps opposite.Usually, after making up with described adhesive material, in resulting body catalyst, the form of metal oxide particle remains unchanged basically.
Used adhesive material can be common any materials as adhesive material in hydrotreating catalyst.The example has silica; Silica-alumina, for example conventional silica-alumina, the aluminium oxide of silica-coating and the silica of aluminum oxide coated; Aluminium oxide, for example (vacation) boehmite or gibbsite; Titanium dioxide; The aluminium oxide of titanium dioxide-coated; Zirconia; Cationic clay or anionic clay, for example saponite, bentonite, kaolin, sepiolite or hydrotalcite; Perhaps their mixture.Preferred adhesive material is aluminium oxide, zirconia, bentonite or their mixture of silica, silica-alumina, aluminium oxide, titanium dioxide, titanium dioxide-coated.Can use these jointing materials itself or use after peptization.
Step (v)
Can make any slurries that randomly contain in the above-mentioned additional materials carry out spray-drying, (fast) drying, grinding, kneading, slurry mixing, dry type mixing or wet mixed or their combination, wet mixed and kneading or slurry mix and spray-dired combination is preferred.Can be after adding above-mentioned (other) material or before (if any), at the solid-liquid after separating, these technology of use are then carried out wetting again before or after heat treatment.
Step (vi)
If necessary, selectively using step (ii) afterwards, the metal oxide particle that selectively is mixed with any above-mentioned additional materials is shaped.This shaping comprises extrudes, granulation, makes pearl and/or spray-drying.Can add common any additive for promoting to be shaped.These additives can comprise: aluminum stearate, surfactant, graphite, starch, methylcellulose, bentonite, polyethylene glycol, PEO or their mixture.If described shaping comprises extrude, granulation, make pearl and/or spray-drying, preferably, have liquid, for example implement this forming step under the condition of water.Preferably, for extruding and/or make pearl, the amount of the liquid in the shaping mixt (being expressed as combustible loss amount (LOI)) is in the scope of 20-80%.
Step (vii)
After selectable drying steps, if necessary, preferably more than 100 ℃, resulting formed catalyst composition can be heat-treated.But heat treatment is optional for method of the present invention.As mentioned above, body catalyst of the present invention has temperature sensitive metastable state six side's phases, and it is easy to be converted into crystal structure.Therefore, preferably being lower than generation under the temperature of the temperature of crystal structure conversion, described metal oxide particle is heat-treated, preferably below 450 ℃, more preferably below 400 ℃, more preferably below 375 ℃, most preferably below 350 ℃.Usually after combination and being shaped, final body catalyst is carried out described heat treatment, but also can heat-treat middle powder, then carry out again wetting.Heat treatment time can change between 0.5～48 hour, can be at inert gas nitrogen for example, and perhaps oxygen-containing gas for example carries out in air or the purity oxygen.Can carry out described heat treatment under the condition of water vapour existing.
Method of the present invention can also comprise vulcanisation step.Usually, by directly after the preparation metal oxide particle, perhaps after any step in additional treatment step (iii)-(vii), most preferably after being configured as the body catalyst of shaping, make described body catalyst and sulfur-containing compound, for example elementary sulfur, hydrogen sulfide, DMDS or inorganic or organic polysulfide compound contact, and vulcanize.Generally can be in position and/or other position carry out described sulfuration.Preferably, carry out described sulfuration in other position, namely before the carbon monoxide-olefin polymeric of sulfuration is put into hydrotreating unit, in independent reactor, carry out described sulfuration.In addition, preferably, all make described carbon monoxide-olefin polymeric sulfuration in other position and original position.
The preferred method of the present invention comprises the following continuous treatment step for preparing body catalyst of the present invention: in the slurries with above-mentioned protic liquid, the first and second compounds are contacted and react; Making resulting metal oxide particle carry out slurry with for example adhesive material mixes; By the described particle of isolated by filtration; The predrying described sediment in selectable centre; Make filter cake with such as adhesive material, mediate, extrude, the materials such as dry, calcining and sulfuration.
Make and characterize with the following method described catalyst:
1. side crushing strength
At first, measure for example length of extrudate particle, then by moveable piston to the extrudate particle load (25lbs in 8.6 seconds) of exerting pressure.Measure the needed power of the described particle of crushing.At least 40 extrudate particles are repeated described process, and calculating mean value is as the power (lbs) of per unit length (mm).Preferably, length is no more than the shaped particles using said method of 7mm.
2. porosity
Such as Paul A.Webb and Clyde Orr, " analytical method of fine granular technology (AnalyticalMethods in Fine Particle Technology) ", (the MicromeriticsInstrument Corporation of Micromeritics Instrument Corp. U.S.A, the nox, GA, USA, 1977, the mode described in the ISBN 0-9656783-0-X was implemented N
2Adsorptiometry.If relate to mean pore sizes MPD, then we can be with reference to following pore-size distribution, it is by from (being disclosed in P.Barrett according to the BJH method, L G.Joyner, P.P.Halenda, The determination of pore volume and area distributions in poroussubstances.I.Computations from nitrogen isotherms, J.Am.Chem.Soc. (nineteen fifty-one), 73, calculate in the desorption curve of nitrogen adsorption isotherm 373-380).By BET method (S.Brunauer, P.H.Emmett and E.Teller, Adsorption of gases in multimolecular layers, J.Am.Chem.Soc. (1938), 60,309-319) mensuration total surface area.
Such as for example Paul A.Webb and Clyde Orr, " Analyticai Methods in Fine ParticleTechnology ", Micromeritics Instrument Corp. U.S.A (Micromeritics Instrument Corporation), the nox, GA, USA, 1977, ISBN 0-9656783-0-X is described, carries out macropore volume by mercury porosimetry and measures, especially for the hole that has more than or equal to the 60nm aperture.
3. the amount of the solid metal compound that adds
Qualitative determination: if when metallic compound exists greater than the form of the particle of visible wavelength with diameter, can by visual examination, easily find the solid metal compound that in technical process of the present invention, exists at least.Certainly, for for example quasi-elastic light scattering of the known method of technical staff (QELS) or near the light forescatering, also can be used for confirming, in the time in technical process of the present invention, when being in dissolved state by all metals.Also can use light scattering (near the light forescatering) to measure median particle diameter.
Quantitative assay: if metallic compound is added as suspension, the described metallic compound that wherein adds is at least part of to be solid state, be determined at the amount of the solid metal compound that adds in the technical process of the present invention by filtering suspension liquid, wherein said suspension is to add under employed condition (temperature of liquid, pH, pressure and amount) in adition process, will collect as solid filter cake by contained all solids material in suspension in this way.Consider from solids and the weight of the filter cake of drying, the weight of solid metal compound can be measured by standard technique.Certainly, if except solid metal compound, also have solid chemical compound in filter cake, for example solid binder materials must deduct the weight of this drying solid adhesive material from the weight of drying solid filter cake.Also can for example atomic absorption spectrum (AAS), XRF, wet-chemical analysis or ICP measure the amount of solid metal compound in the filter cake by standard technique.
If metallic compound is added with hygrometric state or dry state, the described metallic compound that wherein adds is at least part of for solid state, filters normally infeasible.In this case, can think, the weight of solid metal compound equals the weight (based on dry weight) of the corresponding initial metallic compound that adds.The gross weight of all metallic compounds is amounts (based on dry weight) of the initial whole metallic compounds that add, calculates with metal oxide.
4. feature halfwidth
Based on the x-ray diffraction pattern of catalyst, measure the feature halfwidth of oxide catalyst: the feature halfwidth be in 2 θ=53.6 ° (± 0.7 °) and in 2 θ=35 peak width at half peak place at the peak of ° (± 0.7 °).
In order to measure the X-ray diffraction figure, can use the standard powder diffractometer that is equipped with graphite monochromator.Measuring condition can for example be selected as follows:
X-ray generator arranges: 40kV and 40mA,
Wavelength: 1.5418 dusts,
Disperse and anti-scatter slit: v20 (variable),
Detector slit: 0.6nm,
Step sizes: 0.05 (°, 2 θ),
Time/step: 2 seconds,
Instrument: Bruker D5000.
To further explain the present invention by following embodiment.R3 refers to following reaction process, wherein the first and second solid metal compound at least part of solid state that remains all during reaction.R2 refers to following reaction path, and wherein, at least a at least part of in course of reaction in the first or second metallic compound is solid, and at least a in the first or second metallic compound is dissolved state.R1 refers to a kind of following technique, and wherein, all metal components are dissolved state.CBD refers to the compacting bulk density of described catalyst.HT refers to hydrothermal reaction condition.Provided diesel oil hydrogenation in the table 9 and processed the result who tests, wherein RVA and RWA are respectively that relative volume is active and relative weight is active, and it is based on the total catalyst levels that is loaded in the reactor.HDN is hydrodenitrogeneration, and HDS is hydrodesulfurization.Use two kinds of different temperature and pressure experiment conditions 1 and 2 to carry out described test.Suffix 1 or 2 (for example in RWA1 and RWA2) refers to respectively test condition 1 and 2.The result who does not show RWA HDN1 is that so that described measurement is coarse, and the difference between the sample is too little, so that can not differentiate the difference of the catalytic activity between the sample because the nitrogen level in the product is not always the case lowly.In addition, measure sulphur residual level and nitrogen residual level after the hydrotreatment, and in S1, the S2 of table 9 and N2 hurdle, provide.In this test, use the different diesel test procedure that represents with D1, D2, D3, D4 and D5.Reference catalyst C1.2, C1.1, C5.1, C5.2 and C6 respectively the RWA/RVA value in D1, D2, D3, D4 and D5 are defined as 100.Calculate all other RWA/RVA value with respect to these comparative catalyst.
Comparative experiments C1.1 and C1.2 (Ni1.5Mo0.5W0.5R3)
MoO with 115.2g
3The wolframic acid H of (0.8 mole of Mo, FOX company (ex.Aldrich)) and 200g
2WO
4(0.8 mole of W, ex.Aldrich) forms slurries (suspending liquid A) in 6400ml water, and is heated to 90 ℃.Basic nickel carbonate 2NiCO with 282.4g
33Ni (OH)
24H
2O (2.4 moles of Ni, ex.Aldrich) is suspended in the 1600ml water, and is heated to 90 ℃ (suspension B).Employed basic nickel carbonate has 239m in this embodiment and other embodiment
2The BET surface area of/g.In 10 minutes, suspension B is joined in the suspending liquid A, with resulting mixture under 90 ℃ along with continuous stirring is kept 16 hours (spending the night).When this time finishes, with suspension filtered.Its productive rate surpasses 98% (based on the calculated weight of all metal components that are converted into oxide).The adhesive material (based on the gross weight of this carbon monoxide-olefin polymeric) of resulting filter cake and 2.5wt% is carried out wet mixing to be closed.The water content of regulating mixture is the mixture that can extrude in order to obtain, subsequently this mixture is extruded.With resulting solid dry 16 hours (spending the night) under 120 ℃, and 300 ℃ of lower calcinings 1 hour.Make described catalyst vulcanization, and use and test (in table 9, being expressed as C1.2 and C1.1) according to the program of diesel test procedure D1 and D2.
Comparative experiments C2 (Ni1.5Mo1R2)
With 282.4g ammonium heptamolybdate (NH
4)
6Mo
7O
244H
2O (1.6 moles of Mo, ex.Aldrich) is dissolved in the 6400ml water, and at room temperature regulator solution pH is approximately 5.2.Then this solution is heated to 90 ℃ (solution A).Basic nickel carbonate 2NiCO with 282.4g
33Ni (OH)
24H
2O (2.4 moles of Ni, ex.Aldrich) is suspended in the 1600ml water, and this suspension is heated to 90 ℃ (suspension B).In 10 minutes, suspension B is joined in the suspending liquid A, with resulting mixture under 90 ℃ along with continuous stirring was kept 16 hours.Its productive rate is approximately 85%.Described in C1, with resulting filter cake (with the 10wt% adhesive material) extrude, dry, calcining and sulfuration, and use and test according to the program of diesel test procedure D1.
Comparative experiments C3 (Ni1.5W1R2)
Such as the mode described in the C2, Kaolinite Preparation of Catalyst is except employed only a kind of group vib metal component is the tungsten: the ammonium metatungstate (NH that uses 393.6g
4)
6H
2W
12O
40The basic nickel carbonate 2NiCO of (1.6 moles of W, ex.StremChemical) and 282.4g
33Ni (OH)
24H
2O (2.4 moles of Ni) Kaolinite Preparation of Catalyst.All be converted into the calculated weight of their oxide based on all metal components, productive rate is approximately 97%.Such as the mode described in the C1, resulting filter cake is extruded (with the 10wt% adhesive material), dry, calcining and sulfuration, and used diesel test procedure D2 to test.
Comparative experiments C4 (Ni1.5W1R3)
Such as the method described in the contrast experiment C1, Kaolinite Preparation of Catalyst is except only using a kind of group vib metal component: use the molybdenum trioxide (1.6 moles of Mo, ex.Aldrich) of 230.4g and the basic nickel carbonate 2NiCO of 282.4g
33Ni (OH)
24H
2O (2.4 moles of Ni) Kaolinite Preparation of Catalyst.All be converted into the calculated weight of their oxide based on all metal components, its productive rate is about 98%.Such as the mode described in the C1, resulting filter cake is extruded (with the 2.5wt% adhesive material), dry, calcining and sulfuration, and used diesel test procedure D1 to test.
Comparative experiments C5.1 and C5.2 (Ni1Mo0.5W0.5R3)
Such as the mode described in the comparative experiments C1, Kaolinite Preparation of Catalyst is except the Ni that uses lower amount.Use the MoO of 115.2g
3The wolframic acid H of (1.6 moles of Mo, ex.Aldrich), 200g
2WO
4The basic nickel carbonate 2NiCO of (0.8 mole of W, ex.Aldrich) and 188.0g
33Ni (OH)
24H
2O (2.4 moles of Ni) Kaolinite Preparation of Catalyst.Its productive rate is higher than 98%.Make resulting filter cake 120 ℃ of lower dried overnight.Such as the described mode of C1, with resulting filter cake and 10wt% adhesive material extrude, dry, calcining and sulfuration, use diesel test procedure D4 to test (C5.2 in the table 9).Extrudate is pulverized, by sieving separating 40-60 purpose part.Then described material is vulcanized, and use and test (C5.1 in the table 9) according to the program of diesel test procedure D3.
Embodiment E 1 (Ni1.5W1 R3)
Such as the mode described in the C1, Kaolinite Preparation of Catalyst is except only using a kind of group vib metal component: such as the mode described in the C1, use the wolframic acid (1.6 moles of W, ex.Aldrich) of 400g and the basic nickel carbonate 2NiCO of 282.4g
33Ni (OH)
24H
2O (2.4 moles of Ni) Kaolinite Preparation of Catalyst.All be converted into the calculated weight of their oxide based on all metal components, its productive rate is approximately 99%.Such as the described mode of C1, resulting filter cake is extruded (with the 2.5wt% adhesive material), drying, calcining and sulfuration, and used diesel test procedure D1 to test.Its result demonstrates, and the performance of the bimetallic nickel tungsten catalyst of E1 is better than trimetallic catalyst C1.2 (table 9), and the prepared catalyst of preparation method (C3) that also is better than NiMo catalyst (C2 and C4) and passes through approach R2.
Embodiment E 2 (Ni0.75W1 R3 HT)
Similar method described in employing and the C5, preparation Ni/W mol ratio is 0.75: 1 catalyst, except following condition: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.015 mole of Ni) of 1.76g is joined in 100 milliliters the water with the wolframic acid (0.02 mole of W) of 4.99g.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with 10 ℃/minute speed, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then with described material sulfuration, use and test according to the method for diesel test procedure D3.Surprisingly, compare the performance of bimetallic catalyst E2 be improved (table 9) with the trimetallic catalyst of C5.1.
Embodiment E 3 (Ni1W1 R3 HT)
Such as the mode described in the E1, Kaolinite Preparation of Catalyst, except following condition: the Ni/W mol ratio is 0.75: 1, and under self-generated pressure, 150 ℃ reaction temperature, reacts in the autoclave reactor with carry out microwave radiation heating.The nickelous carbonate (0.02 mole of Ni) of the 2.35g wolframic acid (0.02 mole of W) with 4.99g is joined in 100 ml waters.Suspension is joined the sealing Weflon of 275 milliliters of cumulative volumes
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then with described material sulfuration, use and test according to the program of diesel test procedure D3.Surprisingly, C5.1 compares with trimetallic catalyst, and the performance of the bimetallic material of E3 is improved.
Embodiment E 4 (Ni0.5W1 R3 HT)
Such as the mode described in the E1, Kaolinite Preparation of Catalyst, except following condition: the Ni/W mol ratio is 0.5: 1, at the described catalyst of more extensive preparation.The nickelous carbonate (1.4 moles of Ni) of the 164.5g wolframic acid (2.8 moles of W) with 699.6g is joined in 14 premium on currency.Suspension is joined in 5 gallon autoclave, and sealing autoclave is heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.Such as the mode described in the C1, with resulting material and the wet mixing of 10wt% adhesive material close, extrude, dry, calcining and sulfuration, use diesel test procedure D4 to test.
Embodiment E 5 (Ni0.5W0.975Nb0.025 R3 HT)
Such as the described mode of E4, Kaolinite Preparation of Catalyst is except following condition: Nb is joined in the reactant mixture; The mol ratio of Ni: W: Nb is 0.5: 0.975: 0.025, and to prepare more on a large scale described catalyst.The nickelous carbonate (1.4 moles of Ni) of 164.5g is joined in 14 premium on currency with the wolframic acid (2.73 moles of W) of 682.5g and the niobic acid (0.07 mole of Nb) (CBBM industrial group (ex.CBBM Industries)) of 11.19g.Suspension is joined in 5 gallon autoclave, and sealing autoclave is heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.Such as the mode described in the C1, the resulting material of parallel preparation of combination is extruded (with the 10wt% adhesive material), dry, calcining and sulfuration, use diesel test procedure D4 to test.Surprisingly, compare the performance that contains niobium material of E5 be improved (table 9) with trimetallic catalyst C5.2 with bimetallic catalyst E4.
Comparative experiments C6 (Ni1Mo0.5W0.5 R3 HT)
The mol ratio of preparation Ni: Mo: W is 1: 0.5: 0.5 catalyst.Nickelous carbonate (0.02 mole of Ni) and the wolframic acid (0.01 mole of W) of 2.5g and the MoO of 1.44g with 2.35g
3(0.01 mole of Mo) joins in 100 milliliters the water together.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then with described material sulfuration, use diesel test procedure D3 to test.The HDS performance of three metal materials of the hydro-thermal of C6 preparation is lower than the bimetallic nickel tungsten catalyst, particularly test condition 2 times.
Comparative experiments C7 (Ni1W0.5Mo0.5 R3)
Basic nickel carbonate 2NiCO with 188g
33Ni (OH)
24H
2O (1.6 moles of Ni) is suspended in the 8000ml water, and resulting slurry is heated to 60 ℃.Then, the MoO that adds 115.2g
3The wolframic acid H of (0.8 mole Mo) and 200g
2WO
4(0.8 mole W), and the gained slurry is heated to 95 ℃, under this temperature along with continuous stirring is kept approximately 24 hours time.When this time finishes, with suspension filtered.The adhesive material (based on the gross weight of this carbon monoxide-olefin polymeric) of resulting filter cake and 10wt% is carried out wet mixing to be closed.The water content of regulating mixture is the mixture that can extrude in order to obtain, subsequently this mixture is extruded.With resulting solid dry 16 hours (spending the night) under 120 ℃, and 300 ℃ of lower calcinings 1 hour.This extrudate is pulverized, and logical sieving separating goes out 40-60 purpose part.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 6 (R3 Ni1 W1,90)
Wolframic acid H with 50.0g
2WO
4The basic nickel carbonate 2NiCO of (0.2 mole W) and 23.5g
33Ni (OH)
24H
2O (0.2 mole of Ni) forms slurries together in 1 premium on currency.The slurries of two kinds of solids are heated to 90 ℃, and under this temperature along with continuous stirring is kept approximately 20 hours (spending the night).Last in this time, with suspension filtered.With resulting solid dry 16 hours (spending the night) under 120 ℃.With resulting solid granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and when the metal molar ratio is 1, can not obtain highly active catalyst under non-hydrothermal reaction condition.
Embodiment E 7 (Ni1W1 R3 HT125)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 125 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.02 mole of Ni) of 2.35g is joined in 100 milliliters the water with the wolframic acid (0.02 mole of W) of 4.99g.Suspension is joined the sealing Weflon of 275 milliliters of cumulative volumes
TMIn the container, with the speed of 10 ℃/min with carry out microwave radiation heating to 125 ℃, then under self-generated pressure and this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 8 (Ni1W1 R3 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.02 mole of Ni) of the 2.35g wolframic acid (0.02 mole of W) with 4.99g is joined in 100 ml waters.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, with the speed of 10 ℃/min with carry out microwave radiation heating to 150 ℃, then under self-generated pressure and this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 9 (Ni1W1 R3 175)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 175 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.02 mole of Ni) of the 2.35g wolframic acid (0.02 mole of W) with 4.99g is joined in 100 ml waters.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 175 ℃ with the speed of 10 ℃/min, then under self-generated pressure and this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Embodiment E 7～E9 demonstrates, and with reference catalyst C7 and be not that the identical catalyst E6 for preparing under hydrothermal condition compares, hydrothermal condition causes the activity that significantly improves.
Embodiment E 10 (Ni1Nb.025W0.975 R3)
Wolframic acid H with 48.7g
2WO
4The basic nickel carbonate 2NiCO of (0.195 mole W) and 23.5g
33Ni (OH)
24H
2The niobic acid (0.005 mole of Nb) of O (0.2 mole of Ni) and 0.8g forms slurries together in 1 premium on currency.The suspension of three kinds of solids is heated to 90 ℃, and under this temperature, keeps along with continuous stirring the time of 20 hours (spending the night).Last in this time, with suspension filtered.With resulting solid dry 16 hours (spending the night) under 120 ℃.With resulting solid granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 11 (Ni1Nb.05W0.95 R3)
Wolframic acid H with 47.4g
2WO
4The basic nickel carbonate 2NiCO of (0.19 mole W) and 23.5g
33Ni (OH)
24H
2The niobic acid (0.01 mole of Nb) of O (0.2 mole of Ni) and 1.6g forms slurries together in 1 premium on currency.The suspension of three kinds of solids is heated to 90 ℃, and under this temperature, keeps along with continuous stirring the time of 20 hours (spending the night).Last in this time, with suspension filtered.With resulting solid dry 16 hours (spending the night) under 120 ℃.With resulting solid granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 12 (Ni1Nb.075W0.925 R3)
H with the wolframic acid of 46.2g
2WO
4The basic nickel carbonate 2NiCO of (0.185 mole of W) and 23.5g
33Ni (OH)
24H
2The niobic acid (0.015 mole of Nb) of O (0.2 mole of Ni) and 2.4g forms slurries together in 1 premium on currency.The suspension of three kinds of solids is heated to 90 ℃, and under this temperature along with continuous stirring is kept the approximately time of 20 hours (spending the night).Last in this time, with suspension filtered.With resulting solid dry 16 hours (spending the night) under 120 ℃.With resulting solid granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Embodiment E 10～E12 demonstrates, even a small amount of Nb has caused the activity that improves.But because the Ni mol ratio is very low, activity level is quite low.
Embodiment E 13 (Ni1Nb.025W0.975 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.02 mole of Ni) of 2.35g is joined in 100 milliliters the water with the niobic acid (0.0005 mole of Nb) of the wolframic acid (0.0195 mole of W) of 4.87g and 0.080g.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 14 (Ni1Nb.05W0.95 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The niobic acid (0.001 mole of Nb) of the wolframic acid (0.019 mole of W) of the g of nickelous carbonate (0.02 mole of Ni) with 4.74 of 2.35g and 0.16g joined in 100 milliliters the water.It is 275 milliliters sealing Weflon that this suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.
Embodiment E 15 (Ni1Nb.075W0.925 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.02 mole of Ni) of 2.35g is joined in 100 milliliters the water with the niobic acid (0.0015 mole of Nb) of the wolframic acid (0.0185 mole of W) of 4.62g and 0.24g.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting material was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Embodiment E 13～E15 demonstrates, compare with the catalyst E10～E12 of non-hydro-thermal preparation, the niobium catalytic that contains in the hydrothermal condition preparation not only has the activity that significantly improves, and, compare with not containing catalyst a small amount of niobium, under the same conditions preparation, have the activity of very significantly unexpected raising.
Embodiment E 16 (Ni1W1 R3,7 days)
Wolframic acid H with 50.0g
2WO
4The basic nickel carbonate 2NiCO of (0.2 mole of W) and 23.5g
33Ni (OH)
24H
2O (0.2 mole of Ni) forms slurries together in 1 premium on currency.The slurries of two kinds of solids are heated to 90 ℃, and under this temperature, keep along with continuous stirring 7 days time.Last in this time, with suspension filtered.With resulting solid dry 16 hours (spending the night) under 120 ℃.With resulting solid granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and when the reaction time is very long, compares the activity that can obtain to improve with 20 little the reaction times; But, and to be compared by the resulting raising of hydrothermal condition, this raising is quite little.
Embodiment E 17 (Ni1.5W1 R3 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.03 mole of Ni) of the 3.53g wolframic acid (0.02 mole of W) with 4.99g is joined in 100 ml waters.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under self-generated pressure and this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.The result demonstrates, and under hydrothermal condition, when metal molar is higher, can obtain extraordinary result; But higher metal molar is than optional or desirable.
Contrast experiment C8 (Ni0.9W1 R1 90)
The ammonium metatungstate (0.2 mole of W) of 49.2g is dissolved in the 800ml water, and regulator solution pH is approximately 5.2.0.4 mole ammonium hydroxide (approximately 30ml) is joined in this solution, make pH bring up to approximately 9.8.Solution is heated to 90 ℃ (solution A).Be dissolved in by the Nickelous nitrate hexahydrate (0.18 mole of Ni) with 52.5g and prepare the second solution in the 50ml water.Make this solution remain on 90 ℃ (solution B).Speed with 7ml/min dropwise joins solution B in the solution A.With formed suspension agitation 30 minutes, make simultaneously temperature remain on 90 ℃.With this material heat filtering, then in air 120 ℃ of dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then this material was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and in preparation approach R1, when the metal molar ratio is 1 or when lower, also can not obtain highly active catalyst under non-hydrothermal reaction condition.
Contrast experiment C9 (Ni0.9W1 R1 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is 30 minutes.With the ammonium metatungstate (0.04 mole of W) of 9.86g and the about Ammonia of 6ml (0.08 mole of NH
4OH) join in the 100 ml water solution of Nickelous nitrate hexahydrate (0.036 mole of Ni) of 10.48g.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 30 minutes.With the sample cool to room temperature, cross filter solid, washing is 120 ℃ of lower dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and under hydrothermal condition, the catalyst of E8 also has than by the higher activity of the prepared comparative catalyst of approach R1 according to the present invention.
Contrast experiment C10 (Ni1 W1 R2)
Ammonium metatungstate (NH with 49.2g
4)
6H
2W
12O
40(0.2 mole of W) is dissolved in the 800ml water, and at room temperature regulator solution pH is approximately 5.2.Subsequently solution is heated to 90 ℃ (solution A).Basic nickel carbonate 2NiCO with 23.5g
33Ni (OH)
24H
2O (0.2 mole of Ni) is suspended in the water of 200ml, then this suspension is heated to 90 ℃ (suspension B).In 10 minutes, suspension B is joined in the suspending liquid A, with resulting mixture under 90 ℃ along with continuous stirring is kept 16 hours (spending the night).With resulting solid granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and in preparation approach R2, when the metal molar ratio is 1, also can not obtain highly active catalyst under non-hydrothermal reaction condition.
Contrast experiment C11 (Ni1W1 R2 HT150)
At following condition Kaolinite Preparation of Catalyst: under the reaction temperature of self-generated pressure and 150 ℃, react in the autoclave reactor with carry out microwave radiation heating, the reaction time is approximately 6 hours.The nickelous carbonate (0.03 mole of Ni) of 2.35g is joined in 150 milliliters the water with the ammonium metatungstate (0.03 mole of W) of 7.40g.It is 275 milliliters sealing Weflon that suspension is joined cumulative volume
TMIn the container, be heated to 150 ℃ with the speed of 10 ℃/min, then under this temperature along with continuous stirring was kept 6 hours.With the sample cool to room temperature, cross filter solid, 120 ℃ of lower dried overnight.With resulting material granulation, pulverize this particle, go out 40-60 purpose part by sieving separating.Then resulting materials was calcined 1 hour under 300 ℃.Then with described material sulfuration, use diesel test procedure D5 to test.Its result demonstrates, and under hydrothermal condition, the catalyst of E8 also has than by the higher activity of the prepared comparative catalyst of approach R2 according to the present invention.
To all examples measure halfwidths (FWHM), it found that, halfwidth in all embodiment (FWHM) all is lower than 2.5.
Diesel test procedure D1 (diesel test procedure D1)
In the downflow system tubular reactor, catalyst is tested.Each reaction tube contains the 10ml catalyst, and it mixes with the SiC particle of equivalent, and is clipped between the SiC stratum granulosum.Before testing, with the catalyst prevulcanization, it is by using raw material of describing in table 1 to carry out the liquid phase prevulcanization, and it has been impregnated in dimethyl disulphide, and to reach total sulfur content be 3.7wt.%.Then, the catalyst of prevulcanization is tested in the hydrotreatment of the internal combustion engine raw material with performance shown in the table 1:
Table 1
| Gasoline stocks | |
| Sulfur content (%wt) | 1.24 |
| Nitrogen content (ppmwt) | 86 |
| Monoaromatics (%wt) | 16.5 |
| Two aromatic compounds (%wt) | 10.8 |
| Two+-aromatic compound (%wt) | 0.8 |
| Whole aromatic compounds (%wt) | 28.1 |
| The distillation ASTM-D 86 of simulation | |
| Play bubble point | 184 |
| 5% volume (℃) | 218.6 |
| 10% volume (℃) | 231.1 |
| 20% volume (℃) | 250.9 |
| 30% volume (℃) | 264.8 |
| 40% volume (℃) | 276.4 |
| 50% volume (℃) | 286.8 |
| 60% volume (℃) | 298.1 |
| 70% volume (℃) | 309.7 |
| 80% volume (℃) | 324.7 |
| 90% volume (℃) | 345.3 |
| 95% volume (℃) | 360.3 |
| Final boiling point (℃) | 373.8 |
The described catalyst of test under two kinds of conditions shown in the table 2.
Table 2
| Prevulcanization | Condition 1 | Condition 2 | |
| Temperature (℃) | 315 | 320 | 340 |
| Pressure (bar) | 30 | 40 | 20 |
| H 2Ratio (NI/I) with oil | 200 | 300 | 300 |
| LHSV(l/h) | 3.0 | 2.0 | 1.5 |
Diesel test procedure D2
With catalyst to be loaded in the reactor with similar mode described in the D1.Before testing, with the catalyst prevulcanization, it is by using raw material of describing in table 3 to carry out the liquid phase prevulcanization, and it has been impregnated in dimethyl disulphide, and to reach total sulfur content be 3.7wt.%.Then, the catalyst of prevulcanization is tested in the hydrotreatment of the internal combustion engine raw material with performance shown in the table 3:
Table 3
| Gasoline stocks | |
| Sulfur content (%wt) | 1.23 |
| Nitrogen content (ppmwt) | 85 |
| Monoaromatics (%wt) | 16.6 |
| Two aromatic compounds (%wt) | 11.1 |
| Two+-aromatic compound (%wt) | 0.7 |
| Whole aromatic compounds (%wt) | 28.4 |
| The distillation ASTM-D 86 of simulation | |
| Play bubble point | 180 |
| 5% volume (℃) | 220 |
| 10% volume (℃) | 233 |
| 20% volume (℃) | 250 |
| 30% volume (℃) | 262 |
| 40% volume (℃) | 273 |
| 50% volume (℃) | 284 |
| 60% volume (℃) | 295 |
| 70% volume (℃) | 307 |
| 80% volume (℃) | 321 |
| 90% volume (℃) | 341 |
| 95% volume (℃) | 345 |
| Final boiling point (℃) | 354 |
The described catalyst of test under two kinds of conditions shown in the table 4.
Table 4
| Prevulcanization | Condition 1 | Condition 2 | |
| Temperature (℃) | 315 | 315 | 340 |
| Pressure (bar) | 45 | 45 | 20 |
| H 2Ratio (NI/I) with oil | 200 | 200 | 200 |
| LHSV(l/h) | 3.0 | 1.5 | 1.5 |
Diesel test procedure D3
With catalyst to be loaded in the reactor with similar mode described in the D1.Before testing, with the catalyst prevulcanization, it is by using raw material of describing in table 5 to carry out the liquid phase prevulcanization, and it has been impregnated in dimethyl disulphide, and to reach total sulfur content be 3.7wt.%.The catalyst of prevulcanization is tested in the hydrotreatment of the internal combustion engine raw material with performance shown in the table 5:
Table 5
| Gasoline stocks | |
| S(％wt) | 1.2 |
| N(ppmwt) | 84 |
| Whole aromatic compounds (wt%) | 27.8 |
| Polynuclear aromatic compound (PNA) (wt%) | 11.7 |
| Single aromatic series (wt%) | 16.5 |
| Two aromatic compounds (wt%) | 10.8 |
| Three+-aromatic compound (wt%) | 0.8 |
| The distillation ASTM-D 86 of simulation | |
| Play bubble point | 184℃ |
| 5 volume % | 218℃ |
| 10 volume % | 231℃ |
| 30 volume % | 265℃ |
| 50 volume % | 287℃ |
| 70 volume % | 310℃ |
| 90 volume % | 345℃ |
| Final boiling point (℃) | 374℃ |
The described catalyst of test under two kinds of conditions shown in the table 6.
Table 6
| Prevulcanization | Condition 1 | Condition 2 | |
| Temperature (℃) | 320 | 330 | 340 |
| Pressure (bar) | 40 | 40 | 20 |
| H 2Ratio (NI/I) with oil | 300 | 300 | 300 |
| LHSV(l/h) | 3.00 | 2.00 | 1.50 |
Diesel test procedure D4
Described in D3, test these catalyst, except being another air speed in first condition.
| Prevulcanization | Condition 1 | Condition 2 | |
| Temperature (℃) | 320 | 330 | 340 |
| Pressure (bar) | 40 | 40 | 20 |
| H 2: oil ratio example (NI/I) | 300 | 300 | 300 |
| LHSV(l/h) | 3.00 | 1.50 | 1.50 |
Diesel test procedure D5
With catalyst to be loaded in the reactor with similar mode described in the D1.Before testing, with the catalyst prevulcanization, it is by using LGO raw material of describing in table 7 to carry out the liquid phase prevulcanization, and it has been impregnated in dimethyl disulphide, and to reach total sulfur content be 3.7wt.%.The catalyst of prevulcanization is tested in the hydrotreatment of the internal combustion engine raw material with performance shown in the table 8:
Table 7
| Gasoline stocks | |
| S(％wt) | 1.1969 |
| N(ppmwt) | 102 |
| Whole aromatic compounds (%wt) | 28.3 |
| Monoaromatics (%wt) | 16.5 |
| Two aromatic compounds (%wt) | 11.0 |
| Three+-aromatic compound (%wt) | 0.8 |
| The distillation ASTM-D 86 of simulation | |
| Play bubble point | 178.4℃ |
| 5 volume % | 211℃ |
| 10 volume % | 224℃ |
| 30 volume % | 261℃ |
| 50 volume % | 283℃ |
| 70 volume % | 309℃ |
| 90 volume % | 348℃ |
| Final boiling point (℃) | 372℃ |
The described catalyst of test under two kinds of conditions shown in the table 8.
Table 8
| Prevulcanization | Condition 1 | Condition 2 | |
| Temperature (℃) | 320 | 320 | 340 |
| Pressure (bar) | 45 | 45 | 20 |
| H 2Ratio (NI/I) with oil | 200 | 300 | 300 |
| LHSV(l/h) | 3.00 | 3.00 | 1.50 |
Claims (9)
1. for the preparation of the method for the body catalyst that contains nickel tungsten metal oxidic particles, the method comprising the steps of:
(i) form the first solid metal compound contain VIII family metallic nickel and the slurries that contain the second solid metal compound of group vib tungsten in water, described slurries also contain with respect to the total amount of group vib metal less than the second group vib metal of 10 % by mole with respect to the total amount of the group vib metal V family metal less than 10 % by mole;
(ii) in the temperature more than 100 ℃ and being higher than under the pressure of 1 bar, described the first solid metal compound and described the second solid metal compound are reacted, the at least part of solid state that remains of the first solid metal compound and the second solid metal compound in whole course of reaction thus is to form nickel tungsten metal oxidic particles; And
(iii) form body catalyst by described nickel tungsten metal oxidic particles.
2. method according to claim 1 being lower than generation under the temperature of the temperature of crystal structure conversion, is heat-treated described body catalyst.
3. method according to claim 1, wherein, nickel than tungsten metal molar than between 0.2～1.5.
4. method according to claim 1, wherein, described body catalyst has metastable hexagonal structure, and the x-ray diffraction pattern of this metastable hexagonal structure has the angle of diffraction 2 θ at the single reflection peak between 58 °～65 ° and between 32 °～36 ° and the principal reflection peak between 50 °～55 °.
5. method according to claim 4, wherein, described principal reflection peak has the halfwidth less than 2.5 °.
6. method according to claim 1, wherein, described slurries contain to have at least 150m
2The nickel of the carbonate of/g surface area or basic carbonate salt form.
7. method according to claim 1, described body catalyst also contains V family metal, wherein the amount of V family metal with respect to the total amount of group vib metal between 0.1～10 % by mole.
8. be used for the method for hydrocarbon raw material that hydrotreatment comprises the organic compound of sulfur-bearing and nitrogen, the method comprises the step that catalyst that described hydrocarbon raw material and method according to claim 1 are prepared contacts.
9. the method for ultra-deep hydrodesulfuration that is used for the hydrocarbon feed of sulfur-bearing and nitrogen, the method comprise raw material are contacted with the body catalyst that is prepared by method claimed in claim 1.
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| EP06100756.3 | 2006-01-24 | ||
| PCT/EP2006/010300 WO2007048598A2 (en) | 2005-10-26 | 2006-10-25 | A bulk catalyst comprising nickel tungsten metal oxidic particles |
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Families Citing this family (53)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2759044C (en) * | 2009-04-29 | 2017-09-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| DK2576053T3 (en) | 2010-06-01 | 2018-08-06 | Exxonmobil Res & Eng Co | HYDROGEN TREATMENT CATALYSTS AND PREPARATION THEREOF |
| EP2450103A1 (en) | 2010-11-03 | 2012-05-09 | Centre National de la Recherche Scientifique (CNRS) | Novel bulk catalyst precursors and method for obtaining such bulk catalyst precursors |
| US9168519B2 (en) | 2010-11-11 | 2015-10-27 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8658558B2 (en) | 2010-11-11 | 2014-02-25 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8575062B2 (en) | 2010-11-11 | 2013-11-05 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| CN103260758B (en) | 2010-11-11 | 2015-09-02 | 雪佛龙美国公司 | Hydro-conversion multimetal reforming catalyst and preparation method thereof |
| US8586500B2 (en) | 2010-11-11 | 2013-11-19 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8575061B2 (en) | 2010-11-11 | 2013-11-05 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8968534B2 (en) * | 2012-01-31 | 2015-03-03 | Toyota Motor Egineering & Manufacturing North America, Inc. | Water oxidation catalyst |
| CN103240096B (en) * | 2012-02-08 | 2015-02-25 | 中国石油天然气股份有限公司 | Method for preparing mixed metal catalyst |
| SG11201501635QA (en) | 2012-09-05 | 2015-04-29 | Chevron Usa Inc | Hydroconversion multi-metallic catalyst and method for making thereof |
| WO2014158675A1 (en) * | 2013-03-29 | 2014-10-02 | Exxonmobil Research And Engineering Company | Production of low cloud point distillate fuels |
| US10053639B2 (en) * | 2013-11-04 | 2018-08-21 | Exxonmobil Research And Engineering Company | Production of low cloud point diesel fuels and low freeze point jet fuels |
| US10005812B2 (en) | 2015-12-15 | 2018-06-26 | Uop Llc | Transition metal molybdotungsten oxy-hydroxide |
| US10052614B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Mixed metal oxides |
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| US10399063B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Mixed metal oxides |
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| US10449523B2 (en) | 2015-12-15 | 2019-10-22 | Uop Llc | Crystalline bis-ammonia transition metal molybdotungstate |
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| US10399065B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Crystalline transition metal tungstate |
| US10053637B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Transition metal tungsten oxy-hydroxide |
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| AU2017215121B2 (en) | 2016-02-01 | 2020-10-29 | Albemarle Europe Sprl | Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their application |
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| US10882030B2 (en) * | 2017-08-25 | 2021-01-05 | Uop Llc | Crystalline transition metal tungstate |
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| US10737249B2 (en) | 2018-06-26 | 2020-08-11 | Uop Llc | Crystalline transition metal molybdotungstate |
| US11033883B2 (en) | 2018-06-26 | 2021-06-15 | Uop Llc | Transition metal molybdotungstate material |
| US10737248B2 (en) | 2018-06-26 | 2020-08-11 | Uop Llc | Crystalline transition metal tungstate |
| US10688479B2 (en) | 2018-06-26 | 2020-06-23 | Uop Llc | Crystalline transition metal tungstate |
| US10737246B2 (en) | 2018-06-29 | 2020-08-11 | Uop Llc | Poorly crystalline transition metal tungstate |
| US10981151B2 (en) | 2018-06-29 | 2021-04-20 | Uop Llc | Poorly crystalline transition metal molybdotungstate |
| US11213803B2 (en) | 2018-12-13 | 2022-01-04 | Uop Llc | Ammonia-free synthesis for Al or Si based multimetallic materials |
| US10933407B2 (en) | 2018-12-13 | 2021-03-02 | Uop Llc | Ammonia-free synthesis for Al or Si based multimetallic materials |
| KR20200086983A (en) * | 2019-01-10 | 2020-07-20 | 코아텍주식회사 | Metal oxide catalysts for removal of large capacity perfluorinated compounds and its manufacturing method |
| US11426711B2 (en) | 2019-05-22 | 2022-08-30 | Uop Llc | Method of making highly active metal oxide and metal sulfide materials |
| CN111180747B (en) * | 2020-01-06 | 2021-10-01 | 中国科学技术大学 | Anode catalyst, preparation method thereof and alkaline fuel cell |
| CN112978815B (en) * | 2021-03-14 | 2022-11-15 | 北京工业大学 | Preparation method of nickel-tungsten phosphide-nickel-tungsten oxide with heterostructure |
| CN114369847A (en) * | 2022-01-24 | 2022-04-19 | 海南师范大学 | Iron-nickel alloy @ tungsten carbide/carbon composite catalyst, and preparation method and electrocatalysis application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275994A (en) * | 1991-06-17 | 1994-01-04 | Texaco Inc. | Process for preparing a catalyst for removal of hydroprocessing impurities |
| US6402936B1 (en) * | 1999-05-19 | 2002-06-11 | Institut Francais Du Petrole | Catalyst that comprises a partially amorphous Y zeolite, an element of group VB and its use in hydroconversion and hydrorefining of hydrocarbon petroleum feedstocks |
| CN1526478A (en) * | 1999-01-15 | 2004-09-08 | ��˹��ŵ�� | Mixed metal catalyst and use thereof |
| US20050040080A1 (en) * | 1997-07-15 | 2005-02-24 | Riley Kenneth L. | Process for upgrading naphtha |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2642463A (en) * | 1951-01-30 | 1953-06-16 | Du Pont | Metal tungstite catalyzed hydrogenation process |
| US3779903A (en) * | 1967-12-11 | 1973-12-18 | Shell Oil Co | Hydroconversion process with a catalyst having a hydrogenation component composited with a high density alumina |
| US4414102A (en) * | 1981-05-15 | 1983-11-08 | Mobil Oil Corporation | Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil |
| ES2169340T3 (en) * | 1996-12-27 | 2002-07-01 | Inst Francais Du Petrole | HYDRO-REFINED AND HYDROCRACHING CATALYST THAT INCLUDES A MIXED SULFIDE THAT INCLUDES SULFUR, AT LEAST ONE ELEMENT OF GROUP VB AND AT LEAST ONE ELEMENT OF GROUP VIB. |
| FR2758278B1 (en) * | 1997-01-15 | 1999-02-19 | Inst Francais Du Petrole | CATALYST COMPRISING A MIXED SULFIDE AND USE IN HYDRO-REFINING AND HYDROCONVERSION OF HYDROCARBONS |
| US6620313B1 (en) * | 1997-07-15 | 2003-09-16 | Exxonmobil Research And Engineering Company | Hydroconversion process using bulk group VIII/Group VIB catalysts |
| US6162350A (en) * | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
| US6156695A (en) | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| CA2359906C (en) * | 1999-01-15 | 2007-10-23 | Akzo Nobel N.V. | A mixed metal catalyst composition, its preparation and use |
| FR2846574B1 (en) * | 2002-10-30 | 2006-05-26 | Inst Francais Du Petrole | CATALYST AND PROCESS FOR HYDROCRACKING HYDROCARBON LOADS |
| AR043242A1 (en) * | 2003-02-24 | 2005-07-20 | Shell Int Research | PREPARATION AND USE OF A CATALYST COMPOSITION |
| TW200521219A (en) | 2003-07-08 | 2005-07-01 | Shell Int Research | Process to prepare a base oil |
| US7780845B2 (en) * | 2004-04-22 | 2010-08-24 | Exxonmobil Research And Engineering Company | Process to manufacture low sulfur distillates |
| AU2005235711B2 (en) | 2004-04-22 | 2008-11-13 | Albemarle Netherlands B.V. | Hydrotreating catalyst containing a group V metal |
| US20050236304A1 (en) * | 2004-04-22 | 2005-10-27 | Soled Stuart L | Process to manufacture lube oil products |
| US7591942B2 (en) * | 2004-09-22 | 2009-09-22 | Exxonmobil Research And Engineering Company | Bulk bi-metallic catalysts made from precursors containing an organic agent |
-
2006
- 2006-10-25 ES ES06806546T patent/ES2758348T3/en active Active
- 2006-10-25 CA CA2627447A patent/CA2627447C/en active Active
- 2006-10-25 EP EP06806546.5A patent/EP1951427B1/en active Active
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- 2006-10-25 DK DK06806546T patent/DK1951427T3/en active
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- 2006-10-25 EA EA200801186A patent/EA013580B1/en not_active IP Right Cessation
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275994A (en) * | 1991-06-17 | 1994-01-04 | Texaco Inc. | Process for preparing a catalyst for removal of hydroprocessing impurities |
| US20050040080A1 (en) * | 1997-07-15 | 2005-02-24 | Riley Kenneth L. | Process for upgrading naphtha |
| CN1526478A (en) * | 1999-01-15 | 2004-09-08 | ��˹��ŵ�� | Mixed metal catalyst and use thereof |
| US6402936B1 (en) * | 1999-05-19 | 2002-06-11 | Institut Francais Du Petrole | Catalyst that comprises a partially amorphous Y zeolite, an element of group VB and its use in hydroconversion and hydrorefining of hydrocarbon petroleum feedstocks |
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| AU2006308082B2 (en) | 2011-07-07 |
| ES2758348T3 (en) | 2020-05-05 |
| CA2627447C (en) | 2012-08-07 |
| KR20080068882A (en) | 2008-07-24 |
| WO2007048598A3 (en) | 2007-07-19 |
| JP5089597B2 (en) | 2012-12-05 |
| KR101373988B1 (en) | 2014-03-12 |
| AU2006308082A1 (en) | 2007-05-03 |
| DK1951427T3 (en) | 2019-11-11 |
| HUE046591T2 (en) | 2020-03-30 |
| WO2007048598A2 (en) | 2007-05-03 |
| EA013580B1 (en) | 2010-06-30 |
| CN101365538A (en) | 2009-02-11 |
| US8067331B2 (en) | 2011-11-29 |
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| JP2009513325A (en) | 2009-04-02 |
| EA200801186A1 (en) | 2009-02-27 |
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| US20090127165A1 (en) | 2009-05-21 |
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| EP1951427B1 (en) | 2019-09-18 |
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